JPH09324195A - Solvent usable as detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use a solvent comprising a specific fluorine-containing compound capable of eliminating an oily substance without dissolving it, useful as a rinsing agent for cleaning so as to remove a staining oil from various substrate surfaces without causing toxicity and depletion of ozone layer.

SOLUTION: A solvent (A) comprising a compound oil which has properties capable of eliminating an oily substance such as a hardened oil (e.g. a mineral resin, a poly α-olefin or a mineral oil containing an ester dimer) or a (fluorinated) silicone oil, has a chemical structure of the formula HF₂CO(CF₂O)_n(CF₂CF₂O)_mCF₂H ((m) and (n) are each 0-20 and (m) and (n) are each not 0 at the same time), 30-200°C, especially 60-150°C boiling point and the molar ratio of O/C of 0.5-1 is used. Preferably, a solvent obtained by adding a polar substance [e.g. an alcohol, a ketone, an ether, a compound composed of carbon and fluorine (to be concrete, a perfluoroalkane or a hydrofluoroalkane)] in which ≥1wt.% of the substance is dissolved in the solvent and which is liquid at a temperature for use to the solvent A is used.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a solvent that can be used as a rinse agent for cleaning and can remove oil, grease, wax, etc. from the surface, has no toxicity, has no effect on ozone, and has no effect on global warming. Regarding low solvent. More specifically, the present invention relates to a solvent having the above-mentioned characteristics that can remove oily substances, grease, wax, etc. without dissolving them.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION The technical problems to be solved by the present invention are nontoxic,
To make available a solvent having the above mentioned properties. Such problems are necessary because national legislation bans or attempts to ban most solvents due to their effects on ozone.

Examples of solvents that cannot be used due to their influence on ozone include chlorine-containing solvents, chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (H).
CFC). More particularly, the technical problem to be solved by the present invention relates to a solvent which has the above-mentioned properties and which can additionally remove oily substances without dissolving it, and therefore for the recovery of such solvents. The separation step requires only ordinary mechanical equipment such as removing cream or filtering and does not require complicated and costly separation methods such as fractionation or azeotropic distillation. Is.

Another characteristic that the solvent must have is that it is not flammable so as not to compromise safety, storage and transportation problems. In addition to the above properties, at the same time chlorinated solvents or chlorofluorocarbons currently used in washing operations (removal of oily substances by at least 97.0
It was highly desirable to have an available solvent with a combined performance comparable to that of the (wt%).

[0005]

A substance that can be removed without dissolving an oily substance, which is the object of the present invention, was unexpectedly found, and the solvent is a compound of the general formula HF ₂ CO (CF ₂ O). _n (wherein, m and n are integers of 0 to 20, except. where m and n are 0 at the same _{time) (CF 2 CF 2 O)} m CF 2 H having a, 30 ° C. to 200 DEG
It is a solvent which has a boiling point of 60 ° C., preferably 60 ° C. to 150 ° C. and which can remove an oily substance having a molar ratio O / C of 0.5 to 1 without dissolving it.

The present invention also provides the use of the above solvent for removing oily substances and a method for removing oily substances.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The hydrofluoropolyethers described above are generally comprised of a mixture of components having boiling points within the above ranges and having different molecular weights. The hydrofluoropolyethers of this invention are obtained by methods known in the art by decarboxylating the alkali salts obtained by hydrolyzing and salting the corresponding acyl fluorides. For example, the decarboxylation is carried out in the presence of a hydrogen-supplying compound such as water at a temperature of 140-170 ° C. under at least 4 atmospheres (see eg EP 695775 Example).

Oily substances or greases and waxes based on oily substances which can be removed without dissolution include silicone oils, fluorosilicone oils or hydrogenated oils.
Silicone oils are well known and are generally for example 50-30.
It is a polymethylsiloxane having different viscosities of 000 cSt. Examples of the fluorosilicone oil include polyfluoropropylmethyl polysiloxane.

Hardened oil means products based on mineral oils of petroleum origin or synthetic or semi-synthetic oils. Mineral resin,
Mention may be made of mineral oils such as polyalphaolefins, for example dimer esters. Perfluoroalkyl end groups -CF _3, -C ₂ F _5, not be removed without fluoropolyethers containing per fluoropolyether and only one terminal hydrogen having -C ₃ F ₇ dissolves the oily substance Considering the results of the experiments conducted by the present inventors, which are industrially interesting, it can be said that the results according to the present invention were unexpected.

It has been found that it is suitable to add the following additives to the solvents of the invention for oils or their derivatives in order to increase the removal of oily substances, which is also the object of the invention. The additive forming is a polar substance that is liquid at the use temperature and that is soluble in the solvent of this invention by at least 1% by weight.

Higher concentrations of these additives can be utilized, provided they are within the solubility limits. Generally, the concentration used is 5
It is 10% by weight. Examples of the polar substance include alcohols having 1 to 4 carbon atoms, preferably ketones such as isopropyl alcohol, acetone and methyl ethyl ketone, and ethers such as diethyl ether.

Preferred additives are those which contain polar groups in the compound of carbon and fluorine, for example in the perfluoroalkane or hydrofluoroalkane chain, the number of carbons being the liquid one mentioned above due to its solubility. Value. A preferable compound is a compound having 2 to 6 carbon atoms, and examples thereof include CF ₃ CH ₂ OH and (CF ₃ ) ₂ CHOH.

Other preferred compounds are (C_ThreeF₆O),
(C_TwoF_FourO), (CFXO) (where X is F or CF)
_Three), (CR₁R_TwoCF_TwoCF_TwoO) (R in the formula₁
Is R _TwoSame or different from H, F, perfluoroal
Kill C₁~ C_ThreeIt is. ) Selected from
It is a polar substance composed of a alkylene unit. Especially general
Formula, R_f-CFX-LL-CF_Two-R_f-CF_Two-L (R in the formula_fIs the next perfluoroalkane or hydrofluorine
Selected from Luoro alkane, a)-(C_ThreeF₆O)_{m '}(CFXO)_{n '}-(Unit (C_Three
F₆O) and (CFXO) are randomly distributed along the chain
Is a perfluorooxyalkylene unit and has m '
n'is generally a substance having a boiling point of 25 ° C to 300 ° C.
Is an integer such that m '/ is different from n'
n'is between 5 and 40, X is F or CF _ThreeIn
, N'can be 0), b)

[0014]

Embedded image

(Where p ', q'and t'are a)
An integer giving a substance with points, p '/ q'
Is 5 to 0.3, preferably 2.7 to 0.5, and p'is
It may be 0, and q '/ q' + P '+ t' is 1/10.
Equal to or less than, and the t '/ p' ratio is 0.
2-6), c)-(CR₁R_TwoCF_TwoCF_TwoO)_n− (Where R₁When
R_TwoHas the same meaning as given above, and n is a) above.
It is an integer that gives a substance having the indicated boiling point. ) R_fIs -OR when monofunctional_ThreeType (R_ThreeIs Perfu
Luoroalkyl C₁~ C _ThreeIs an end group of
L is a group containing a polar group. A compound having
No. In the above formula, L is especially -CH_TwoOH;-
CH_TwoOCH_TwoCH_TwoOH; -CH_Two(OCH_TwoC
H_Two)_{n '''}OR '(in the formula, n' '' is an integer of 2 to 15)
R'is H, CH_Three, COCH_Three; -CONHCH_Two
CH_TwoIt is OH).

Preferred additives have a R _f -CFX-L in which R _f has the structure a). The above fluoropolyethers can be obtained by methods well known in the art (eg, US Pat. Nos. 3,665,041, 2,242,218, 3,715,378 and European Patents). No. 239,123). Functionalized polyfluoroethers are described, for example, in European Patent No. 14
It can be obtained according to the method described in US Pat. No. 8,482 and US Pat. No. 3,810,874.

Perfluoroalkanes are generally 4 to 2
It has 0 carbon atoms, preferably 8 to 12 carbon atoms. Hydrofluoroalkanes have the same structure as perfluoroalkanes or have one or more hydrogens at the ends.
The solvent of this invention can remove oily substances by 97% or more. The solvent remaining on the substrate can be easily removed by evaporation.

The substrate that can be treated with the solvent of the present invention may be either organic type or inorganic type, and examples thereof include metals, ceramics or glass materials, and polymer substrates.
The oily substance can be removed by a known technique such as dipping or spraying. In the case of immersion, the contact of the solvent of the invention with the surface to be cleaned is preferably carried out using an ultrasonic bath in order to more effectively remove the solid contaminants.

[0019]

The present invention will now be described by way of examples, which do not limit the scope of the present invention.

Example 1 Deoiling: Removal of oily substance As a solvent (HFPE), the following formula HF ₂ CO (CF ₂ O) _n (CF ₂ CF ₂ O) _n CF ₂
H 2 was used. This product has a boiling point range of 100 ° C to 120 ° C.
And the number average molecular weight Mn is 380 and the O / C ratio is 0.66.
It is.

HFPE having different molecular weights
It consists of a mixture. The ability to remove oily substances was tested by the following method. A drop of the oily product was poured onto the bottom of the glass crystallization vessel and HFPE was added slowly to flow along the vessel wall. The behavior of the oil droplets was then observed: -the test is considered positive if the oil droplets are removed from the bottom of the container; -the test is negative if the oil droplets remain at the bottom or only partially removed. Is.

The deoiling test was carried out using the following oils. -Me silicone oil (50 cSt Dow Corning) -Me silicone oil (500 cSt Dow Corning) -Fluoro silicone oil (FS1265; trade name, Dow Corning) -Silicone oil (DC200; trade name, Dow Corning) -Dearomatization resin (D40) Trade name, exon) -PAO (polyalphaolefin) (40 cSt, Itec; trade name) -diester (PRIOLUBE 396)
7; tradename, Uni Chem International) deoiling test HFPE pure and HFPE the formula _{CF 3 O (C 3 F 6} O) m '(CFXO) n' CF 2 CF 2 (0CH 2 CH 2) n ''_'OH (wherein X is F or CF _3, n''' is 5 to 6, m '+
n'is 4 having a number average molecular weight Mn of 1100)) and a mixture with a nonionic additive.

The additives were used when only partial removal of oil droplets by HFPE occurred. The additive concentration used in Example 1 was 1% by weight. The non-ionic fluorine-containing additive is preferably a polar solvent such as alcohol or ketone to avoid flammability problems. The HFPE / additive mixture has no flash point. The results of the deoiling test are shown in Table 1.

Example 2 (Comparative) The deoiling test described in Example 1 above for comparison purposes was carried out with the following: - the formula _{CF 3 - (OCF (CF 3} ) CF 2) n (OC
F ₂ ) _m- OCF ₃ (n / m = 40 and boiling point 90 ° C. and number average molecular weight Mn = 460) PFPE (Galden Y) -formula C ₆ F ₁₄ and boiling point 59 ° C. PFC-1,1 , 2-trichlorotrifluoroethane (CFC
-113) The results are shown in Table 1.

[0025]

[Table 1]

Example 3 The HFPE described in Example 1 was used as a ceramic substrate (chip).
Used to test the ability to remove silicone oil from the. The method is as follows. A known amount of silicone oil is evenly applied to the electronic components. The electronic components are weighed with an analyzer and then contacted with HFPE.

After soaking for 5 minutes, the parts are dried for 1 hour at room temperature so that the solvent is completely removed and then weighed again. Test results are expressed as% oil removed. The test conditions are as follows. Room temperature 20 ° C, amount of oil 0.1g, H
The amount of FPE is 30 ml. The oils used were: -Me silicone oil (500 cSt) -Fluorosilicone (FS1265; trade name, Dow Corning) -Silicone oil (DC200; trade name, Dow Corning) The results are shown in Table 2.

Example 4 (Comparative) The same removal test as in Example 3 was repeated with the following liquids. -PFPE Galden of Example 2 Y-1,1,2-trichlorotrifluoroethane (CFC)
-113) -The PFC results of Example 2 are shown in Table 2.

[0029]

[Table 2]

As can be seen by comparing the results of Example 3 and Example 4, the HFPE of the present invention has an effect comparable to that of CFC-113 and can remove silicon oil. Moreover, HFPE has the advantage of removing the oil without dissolving it, and HFPE can be recovered by simple filtration. Distillation is the only means of solvent recycling since the oil goes into solution with the solvent normally used.

[0031]

According to the present invention, it can be used as a rinse agent for cleaning and can remove oil, grease, wax and the like from the surface, has no toxicity, has no effect on ozone, and has no effect on global warming. A low solvent can be provided. Further, according to the present invention, it is possible to provide a solvent capable of removing an oily substance, grease, wax and the like without dissolving them.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C11D 7:30 7:26) (72) Inventor Gianfranco Spataro Italy, Milan, Risone, Via Mazzini 53 (72) Inventor Giuseppe Marcioni Italy, Milan, Via Valerie Neri 8

Claims (13)

[Claims] 1. The general formula HF ₂ CO (CF ₂ O) _n (CF ₂ CF ₂ O) _m CF ₂ H (wherein m and n are integers from 0 to 20, provided that m and n are 0 at the same time) And 30 ° C to 200 ° C.
Use of a solvent which has a boiling point of C and has a molar ratio O / C of between 0.5 and 1 and which can remove oily substances without dissolving them. 2. Use of a solvent according to claim 1 having a boiling point between 60 ° C. and 150 ° C. 3. Use of a solvent according to claim 1 or 2, wherein the oily substance is silicone oil, fluorinated silicone oil or hydrogenated oil. 4. Use of a solvent according to claim 3 wherein the hardened oil is petroleum or a mineral oil derived from synthetic or semi-synthetic oils. 5. Use of a solvent according to claim 4, wherein the hardened oil is selected from mineral resins, polyalphaolefins, mineral oils with ester dimers. 6. Dissolved in the solvent at least 1% by weight,
Use of a solvent according to any one of claims 1 to 5 wherein a polar substance which is liquid at the temperature of use is used as an additive. 7. Use of a solvent according to claim 6, wherein the additive is selected from alcohols, ketones, ethers and compounds consisting of carbon and fluorine. 8. Use of a solvent according to claim 7, wherein the carbon and fluorine additive is selected from perfluoroalkanes or hydrofluoroalkanes. 9. An additive comprising carbon and fluorine is (C ₃ F
₆ O), (C ₂ F ₄ O), (CFXO) [wherein X is F or CF ₃ ], (CR ₁ R ₂ CF ₂ CF ₂ O) [R ₁ is the same or different from R ₂ and is H, F, is selected from polar substances consisting of perfluoroalkyl C ₁ -C ₃ a is] selected from the fluorooxyalkylene units, the use of solvents by claim 7. 10. The additive is selected from compounds of the following general formula:
Selected, R_f-CFX-LL-CF_Two-R_f-CF_Two-L (R in the formula_fIs the next perfluoroalkane or hydrofluorine
Selected from Luoro alkane, a)-(C_ThreeF₆O)_{m '}(CFXO)_{n '}-(Unit (C_Three
F₆O) and (CFXO) are randomly distributed along the chain
Is a perfluorooxyalkylene unit and has m '
n'is generally a substance having a boiling point of 25 ° C to 300 ° C.
Is an integer such that m '/ is different from n'
n'is between 5 and 40, X is F or CF _ThreeIn
, N'can also be 0), b)(Wherein p ', q'and t'are a)
It is an integer that gives quality, and p '/ q' is 5 to 0.3.
It is preferably 2.7 to 0.5 and p'is 0
Well, q '/ q' + P '+ t' is equal to 1/10
Or smaller than that, and the t '/ p' ratio is 0.2-6.
), C)-(CR₁R_TwoCF_TwoCF_TwoO)_n− (Where R₁When
R_TwoHas the same meaning as given above, and n is a) above.
It is an integer that gives a substance having the indicated boiling point. ) R_fIs -OR when monofunctional_ThreeType (R_ThreeIs Perfu
Luoroalkyl C₁~ C _ThreeIs an end group of
L is a group containing a polar group. ) Use of a solvent according to any one of claims 7-9. 11. L is —CH ₂ OH; —CH ₂ OCH
_{2 CH 2 OH; -CH 2 (} OCH 2 CH 2) n '''OR'
(In the formula, n ′ ″ is an integer of 2 to 15, and R ′ is H, CH.
₃ , COCH ₃ ; -CONHCH ₂ CH ₂ OH)
Use of a solvent according to claim 9 selected from 12. The solvent is R _f --CFX-L (wherein R _f --CFX-L _).
Has the structure of a) above).
Use of solvent according to 1. 13. A solvent capable of removing the oily substance according to claims 6 to 12 without dissolving it.